TW201930495A - Photoresist topcoat compositions and methods of processing photoresist compositions - Google Patents

Photoresist topcoat compositions and methods of processing photoresist compositions Download PDF

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TW201930495A
TW201930495A TW107144364A TW107144364A TW201930495A TW 201930495 A TW201930495 A TW 201930495A TW 107144364 A TW107144364 A TW 107144364A TW 107144364 A TW107144364 A TW 107144364A TW 201930495 A TW201930495 A TW 201930495A
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photoresist
polymer
composition
topcoat
general formula
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TWI702263B (en
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艾維戴爾 考爾
昌毅 吳
喬舒亞A 凱茲
李明琦
桃樂絲 康
侯希森
聰 劉
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美商羅門哈斯電子材料有限公司
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09D133/00Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/02Homopolymers or copolymers of acids; Metal or ammonium salts thereof
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    • C09D133/00Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04Homopolymers or copolymers of esters
    • C09D133/06Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
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    • C09D133/00Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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    • C09D133/00Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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    • C09D7/65Additives macromolecular
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
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    • G03F7/004Photosensitive materials
    • G03F7/0046Photosensitive materials with perfluoro compounds, e.g. for dry lithography
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    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
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    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/09Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
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    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
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    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/16Coating processes; Apparatus therefor
    • G03F7/162Coating on a rotating support, e.g. using a whirler or a spinner
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    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20Exposure; Apparatus therefor
    • G03F7/2041Exposure; Apparatus therefor in the presence of a fluid, e.g. immersion; using fluid cooling means
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    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26Processing photosensitive materials; Apparatus therefor
    • G03F7/30Imagewise removal using liquid means
    • G03F7/32Liquid compositions therefor, e.g. developers
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Abstract

Photoresist topcoat compositions, comprising: a first polymer that is aqueous base soluble and is present in an amount of from 70 to 99 wt% based on total solids of the composition; a second polymer comprising a repeat unit of general formula (IV) and a repeat unit of general formula (V): wherein: R5 independently represents H, halogen atom, C1-C3 alkyl, or C1-C3 haloalkyl; R6 represents linear, branched or cyclic C1 to C20 fluoroalkyl; R7 represents linear, branched or cyclic C1 to C20 fluoroalkyl; L3 represents a multivalent linking group; and m is an integer of from 1 to 5; wherein the second polymer is free of non-fluorinated side chains; and wherein the second polymer is present in an amount of from 1 to 30 wt% based on total solids of the composition and a solvent. The invention finds particular applicability in the manufacture of semiconductor devices.

Description

光阻劑面塗層組合物及處理光阻劑組合物之方法Photoresist top coating composition and method for processing photoresist composition

本發明係關於可以施用於光阻劑組合物之上之光阻劑面塗層組合物。本發明尤其適用作用於形成半導體裝置之浸沒式光微影製程(immersion lithography process)中之面塗層。The present invention relates to a photoresist top coating composition that can be applied to the photoresist composition. The invention is particularly suitable for use as a top coat in an immersion lithography process for forming a semiconductor device.

光阻劑用於將影像轉印至基板上。在基板上形成光阻劑層並且接著經由光遮罩使光阻劑層暴露於活化輻射源。光遮罩具有對活化輻射不透明之區域及對活化輻射透明之其他區域。暴露於活化輻射提供光阻劑塗料之光誘導化學轉化,由此將光遮罩之圖案轉印至經光阻劑塗佈之基板上。在暴露之後,對光阻劑進行烘烤並且藉由與顯影劑溶液接觸以使其顯影,從而得到允許選擇性加工基板之凸紋影像。Photoresist is used to transfer the image to the substrate. A photoresist layer is formed on the substrate and the photoresist layer is then exposed to a source of activating radiation via a photomask. The photomask has areas that are opaque to the activating radiation and other areas that are transparent to the activating radiation. Exposure to activating radiation provides photo-induced chemical conversion of the photoresist coating, thereby transferring the pattern of the photomask onto the photoresist-coated substrate. After exposure, the photoresist is baked and brought into contact with a developer solution to develop it, thereby obtaining a relief image allowing selective processing of the substrate.

用於在半導體裝置中達成奈米(nm)級特徵元件大小之一個方法係使用較短波長的光。然而,找到在193 nm以下透明之材料的難度產生浸沒式光微影製程以藉由使用液體增加透鏡之數值孔徑來將更多光聚焦至膜中。浸沒式光微影在成像裝置(例如ArF光源)之最後一個表面與基板例如半導體晶圓上之第一表面之間採用相對較高之折射率液體,通常係水。One method for achieving nanometer (nm) -level feature size in semiconductor devices is to use shorter wavelength light. However, the difficulty in finding transparent materials below 193 nm creates an immersion photolithography process to focus more light into the film by using a liquid to increase the numerical aperture of the lens. Immersion photolithography uses a relatively high refractive index liquid between the last surface of the imaging device (such as an ArF light source) and a substrate such as a first surface on a semiconductor wafer, usually water.

在浸沒式光微影中,浸沒流體與光阻劑層之間的直接接觸可以引起光阻劑之組分浸出至浸沒流體中。此種浸出可以造成光學透鏡之污染並且引起浸沒流體之有效折射率及透射特性之變化。為了解決此問題,在浸沒流體與底層光阻劑層之間引入光阻劑面塗層作為障壁後者。In immersion photolithography, direct contact between the immersion fluid and the photoresist layer can cause the components of the photoresist to leach into the immersion fluid. Such leaching can cause contamination of the optical lens and cause changes in the effective refractive index and transmission characteristics of the immersion fluid. To solve this problem, a photoresist topcoat is introduced as a barrier between the immersion fluid and the underlying photoresist layer.

針對給定掃描速度展現低後退接觸角(receding contact angle,RCA)之面塗層可以導致水印缺陷(water mark defect)。此等缺陷產生於暴露頭移動過晶圓留下水滴之時。因此,由於抗蝕劑組分浸出至水滴中,所以抗蝕劑敏感性改變,並且水可以滲透至底層抗蝕劑中。已經例如在以下各項中提出使用自隔離面塗層組合物:Daniel P. Sanders等人之《用於浸沒式光微影之自隔離材料(Self-segregating Materials for Immersion Lithography)》,《抗蝕劑材料及加工技術之進展XXV(Advances in Resist Materials and Processing Technology XXV)》,《SPIE會議記錄(Proceedings of the SPIE)》,第6923卷,第692309-1 - 692309-12頁(2008),以及Gallagher等人之美國專利申請公開案第2007/0212646A1號及Wang等人之美國專利申請公開案第2010/0183976A1號。自隔離面塗層在理論上允許在浸沒流體與光阻劑界面處之具有所期望特性之經調整材料,例如在浸沒流體界面處之改進水後退接觸角,並且允許在光阻劑界面處之更快掃描速度及良好的顯影劑溶解度。A topcoat that exhibits a low receding contact angle (RCA) for a given scanning speed can cause water mark defects. These defects occur when the exposure head moves past the wafer and leaves water droplets. Therefore, since the resist component is leached into water droplets, the sensitivity of the resist changes, and water can penetrate into the underlying resist. The use of self-isolating topcoat compositions has been proposed, for example, in Daniel P. Sanders et al., "Self-segregating Materials for Immersion Lithography", "Etching Advances in Resist Materials and Processing Technology XXV (Proceedings of the SPIE), Volume 6923, Pages 692309-1-692309-12 (2008), and Gallagher et al. US Patent Application Publication No. 2007 / 0212646A1 and Wang et al. US Patent Application Publication No. 2010 / 0183976A1. Self-isolating topcoats theoretically allow adjusted materials with desired characteristics at the immersion fluid-photoresist interface, such as improved water receding contact angles at the immersion fluid interface, and allow Faster scanning speed and good developer solubility.

然而,在浸沒式光微影中使用面塗層存在各種挑戰。視諸如面塗層折射率、厚度、酸性、與抗蝕劑之化學相互作用以及浸泡時間等特徵而定,面塗層可以影響例如加工窗口、臨界尺寸(CD)變化以及抗蝕劑輪廓中之一種或多種。另外,使用面塗層可能不利地影響裝置良率,此歸因於例如微橋接或妨礙恰當的抗蝕劑圖案形成之其他圖案化缺陷。雖然出於增加後退接觸角之目的,聚合物在面塗層/浸沒流體界面處之更大疏水性似乎係期望的,但通常理解高疏水性聚合物可能對顯影劑溶解速率具有不利影響,導致圖案化缺陷。因此,在面塗層組合物中使用高度氟化之聚合物可能帶來挑戰。However, the use of topcoats in immersion photolithography presents various challenges. Depending on characteristics such as the refractive index, thickness, acidity, chemical interaction with the resist, and immersion time of the topcoat, the topcoat can affect, for example, processing windows, critical dimension (CD) changes, and One or more. In addition, the use of a topcoat may adversely affect device yield due to, for example, micro-bridges or other patterning defects that prevent proper resist pattern formation. Although greater hydrophobicity of the polymer at the topcoat / immersion fluid interface seems to be desirable for the purpose of increasing receding contact angle, it is generally understood that highly hydrophobic polymers may have an adverse effect on the dissolution rate of the developer, leading to Patterned defects. Therefore, the use of highly fluorinated polymers in topcoat compositions can present challenges.

本領域一直需要改進之光阻劑面塗層組合物及利用解決了與目前先進技術相關之一種或多種問題的此類材料之光微影方法。There is a continuing need in the art for improved photoresist topcoat compositions and photolithographic methods utilizing such materials that solve one or more of the problems associated with current advanced technology.

根據本發明之第一態樣,提供光阻劑面塗層組合物。所述組合物包括:第一聚合物,其係水性鹼溶性的並且以所述組合物之總固體計以70至99 wt%之量存在;第二聚合物,其包括具有通式(IV)之重複單元及具有通式(V)之重複單元:其中:R5 獨立地表示H、鹵素原子、C1-C3烷基或C1-C3鹵烷基;R6 表示直鏈、分支鏈或環狀C1至C20氟烷基;R7 表示直鏈、分支鏈或環狀C1至C20氟烷基;L3 表示多價連接基團;並且m係1至5之整數;其中第二聚合物不含非氟化側鏈;並且其中第二聚合物之存在量以所述組合物之總固體計係1至30 wt%;及溶劑。According to a first aspect of the present invention, a photoresist top coating composition is provided. The composition includes: a first polymer that is aqueous alkali-soluble and is present in an amount of 70 to 99 wt% based on the total solids of the composition; a second polymer that includes a compound having the general formula (IV) Repeating units and repeating units of general formula (V): Wherein: R 5 independently represents H, halogen atom, C1-C3 alkyl or C1-C3 haloalkyl; R 6 represents straight, branched or cyclic C1 to C20 fluoroalkyl; R 7 represents straight, branched Chain or cyclic C1 to C20 fluoroalkyl; L 3 represents a polyvalent linking group; and m is an integer from 1 to 5; wherein the second polymer does not contain non-fluorinated side chains; and wherein the second polymer is present The amount is 1 to 30 wt% based on the total solids of the composition; and the solvent.

根據本發明之另一態樣,提供經塗佈基板。經塗佈基板包括:基板上之光阻劑層;及由光阻劑層上的如本文所描述之光阻劑面塗層組合物形成之面塗層。According to another aspect of the present invention, a coated substrate is provided. The coated substrate includes: a photoresist layer on the substrate; and a topcoat layer formed from the photoresist topcoat composition as described herein on the photoresist layer.

根據本發明之另一態樣,提供加工光阻劑組合物之方法。所述方法包括:(a)將光阻劑組合物施用於基板上以形成光阻劑層;(b)在光阻劑層上施用如本文所描述之光阻劑面塗層組合物以形成面塗層;(c)使面塗層及光阻劑層暴露於活化輻射;並且(d)使所暴露之面塗層及光阻劑層與顯影劑接觸以形成抗蝕劑圖案。According to another aspect of the present invention, a method for processing a photoresist composition is provided. The method includes: (a) applying a photoresist composition to a substrate to form a photoresist layer; (b) applying a photoresist topcoat composition as described herein on the photoresist layer to form A top coat; (c) exposing the top coat and photoresist layer to activating radiation; and (d) contacting the exposed top coat and photoresist layer with a developer to form a resist pattern.

本發明之面塗層組合物包括第一水性基礎聚合物、第二氟化聚合物、溶劑並且可以包含一種或多種額外的視情況選用之組分。施用於光阻劑層上的本發明之面塗層組合物可以最小化或防止光阻劑層的組分遷移至用於浸沒式光微影製程之浸沒流體中。在本發明之較佳面塗層組合物中,第一聚合物及第二聚合物係自隔離聚合物。如本文所使用的術語「浸沒流體」係指介於暴露工具的透鏡與經光阻劑塗佈之基板之間的流體(通常係水)以進行浸沒式光微影。The topcoat composition of the present invention includes a first aqueous base polymer, a second fluorinated polymer, a solvent, and may include one or more additional optional components. The topcoat composition of the present invention applied on the photoresist layer can minimize or prevent the components of the photoresist layer from migrating into the immersion fluid used in the immersion photolithography process. In the preferred topcoat composition of the present invention, the first polymer and the second polymer are self-isolating polymers. The term "immersion fluid" as used herein refers to a fluid (usually water) between the lens of an exposed tool and a substrate coated with a photoresist for immersion photolithography.

此外如本文所使用,若相對於經相同方式處理但不存在面塗層組合物層的相同光阻劑系統而言,在使用面塗層組合物時在浸沒流體中偵測到減少量的酸或有機材料,則認為面塗層抑制光阻劑材料遷移至浸沒流體中。可以在暴露於光阻劑(存在及不存在外塗佈面塗層組合物層)之前,接著在光微影處理光阻劑層(存在及不存在外塗佈面塗層組合物層)並且進行穿過浸沒液體的暴露之後,經由浸沒流體的質譜分析進行浸沒流體中之光阻劑材料的偵測。較佳地,面塗層組合物使浸沒流體中所殘留之光阻劑材料(例如如藉由質譜分析所偵測到的酸或有機物)相對於不採用任何面塗層(亦即浸沒流體直接接觸光阻劑層)的相同光阻劑而言減少至少10%,更佳地,面塗層組合物使浸沒流體中所殘留之光阻劑材料相對於不採用面塗層的相同光阻劑而言減少至少20%、50%或100%。Also as used herein, a reduced amount of acid is detected in the immersion fluid when using a topcoat composition, as compared to the same photoresist system that is treated in the same manner but without a topcoat composition layer. Or organic materials, the topcoat is believed to inhibit the migration of the photoresist material into the immersion fluid. The photoresist layer (presence and absence of an overcoat topcoat composition layer) may be treated with photolithography before exposure to the photoresist (with and without an overcoat topcoat composition layer) and After exposure through the immersion fluid, detection of the photoresist material in the immersion fluid is performed by mass spectrometric analysis of the immersion fluid. Preferably, the topcoat composition allows the photoresist material remaining in the immersion fluid (for example, an acid or an organic substance as detected by mass spectrometry) to be compared to the case where no topcoat is used (that is, the immersion fluid is directly Contact the photoresist layer) by at least 10% for the same photoresist, and more preferably, the topcoat composition makes the photoresist material remaining in the immersion fluid relative to the same photoresist without the topcoat In terms of reductions of at least 20%, 50% or 100%.

本發明之較佳面塗層組合物可以允許改進在浸沒式光微影製程中至關重要的各種水接觸角特徵中之一種或多種,例如在浸沒流體界面處的靜態接觸角、後退接觸角、前進接觸角以及滑動角。面塗層組合物提供例如在水性鹼顯影劑中針對層的暴露與未暴露區域具有極佳顯影劑溶解度的面塗層。較佳的面塗層組合物可以展現出有益的圖案缺陷水準。The preferred topcoat composition of the present invention may allow one or more of various water contact angle characteristics, such as static contact angles and receding contact angles at the immersion fluid interface, to be improved in immersion photolithography processes. , Forward contact angle and sliding angle. The topcoat composition provides, for example, a topcoat having excellent developer solubility for exposed and unexposed areas of the layer in an aqueous alkaline developer. The preferred topcoat composition can exhibit a beneficial level of pattern defects.

所述組合物可以用於乾式光微影中或更通常用於浸沒式光微影製程中。暴露波長除了受到光阻劑組合物之限制之外,不受特定限制,並且248 nm或低於200 nm諸如193 nm或EUV波長(例如13.4 nm)係典型的。The composition can be used in dry photolithography or more commonly in immersion photolithography processes. The exposure wavelength is not specifically limited except that it is limited by the photoresist composition, and 248 nm or less than 200 nm such as 193 nm or EUV wavelength (for example, 13.4 nm) is typical.

適用於本發明之聚合物係水性鹼溶性的以使得由所述組合物形成之面塗層可以在抗蝕劑顯影步驟中使用水性鹼性顯影劑移除,所述水性鹼性顯影劑係例如氫氧化四級銨溶液,例如氫氧化四甲基銨(TMAH),通常係0.26 N水性TMAH。適當地,不同之聚合物可以以不同的相對量存在。The polymer-based aqueous alkali-soluble suitable for the present invention is such that the top coat formed from the composition can be removed using an aqueous alkaline developer in a resist developing step, such as Quaternary ammonium hydroxide solutions, such as tetramethylammonium hydroxide (TMAH), are usually 0.26 N aqueous TMAH. Suitably, different polymers may be present in different relative amounts.

本發明之面塗層組合物之聚合物可以含有各種重複單元,包含例如以下各項中之一種或多種:疏水基團;弱酸基團;強酸基團;分支鏈視情況經取代之烷基或環烷基;氟烷基;或極性基團,諸如酯基、醚基、羧基或磺醯基。聚合物之重複單元上的特定官能基的存在將視例如聚合物之預期官能度而定。如本文所使用的「經取代之」係指使一個或多個氫原子經一個或多個取代基置換,所述取代基例如選自羥基、鹵素(亦即F、Cl、Br、I)、C1-C10烷基、C6-C10芳基或包括前述物質中之至少一種的組合。The polymer of the top coating composition of the present invention may contain various repeating units including, for example, one or more of the following: a hydrophobic group; a weak acid group; a strong acid group; a branched chain optionally substituted alkyl or Cycloalkyl; fluoroalkyl; or polar groups such as ester, ether, carboxy, or sulfonyl. The presence of specific functional groups on the repeating unit of the polymer will depend on, for example, the intended functionality of the polymer. "Substituted" as used herein refers to the replacement of one or more hydrogen atoms with one or more substituents, such as selected from hydroxyl, halogen (ie, F, Cl, Br, I), C1 -C10 alkyl, C6-C10 aryl or a combination comprising at least one of the foregoing.

面塗層組合物之聚合物可以含有在光微影處理期間具有反應性的一種或多種基團,例如可以在存在酸及熱之情況下經歷裂解反應的一種或多種光酸不穩定基團,諸如酸不穩定酯基(例如,諸如藉由丙烯酸第三丁酯或第三丁基甲基丙烯酸酯、金剛烷基丙烯酸酯之聚合得到之第三丁基酯基)及/或諸如藉由乙烯基醚化合物之聚合得到之縮醛基。此類基團的存在可以使得一種或多種相關聚合物更加可溶於顯影劑溶液中,由此有助於顯影處理期間的顯影性及面塗層的移除。The polymer of the top coating composition may contain one or more groups that are reactive during photolithography, such as one or more photoacid-labile groups that can undergo a cleavage reaction in the presence of acid and heat, Such as acid labile ester groups (for example, such as third butyl ester groups obtained by polymerization of third butyl acrylate or third butyl methacrylate, adamantyl acrylate) and / or such as by vinyl ether An acetal group obtained by the polymerization of a compound. The presence of such groups can make one or more related polymers more soluble in the developer solution, thereby facilitating developability during the development process and removal of the topcoat.

所述聚合物可以有利地進行選擇以調整面塗層的特徵,並且每個特徵一般服務於一個或多個目標或功能。此類功能包含例如以下各項中之一種或多種:光阻劑輪廓調節、面塗層表面調節、減少缺陷以及減少面塗層與光阻劑層之間的界面混合。The polymers can be advantageously selected to adjust the characteristics of the topcoat, and each characteristic generally serves one or more goals or functions. Such functions include, for example, one or more of the following: photoresist profile adjustment, topcoat surface adjustment, defect reduction, and interfacial mixing between the topcoat and photoresist layer.

第一(基質)聚合物係水性鹼溶性的。基質聚合物較佳包括具有通式(I)之重複單元及具有通式(II)之重複單元:其中:R1 獨立地表示H、鹵素原子、C1-C3烷基或C1-C3鹵烷基,通常係H或甲基;R2 表示視情況經取代之直鏈、分支鏈或環狀C1-C20烷基,通常係C1-C12烷基;L1 表示單鍵或多價連接基團,例如選自以下各項:視情況經取代之脂族物諸如C1-C6伸烷基及視情況經取代之芳族物諸如C5-C20芳族物以及其組合,及選自-O-、-S-、-COO-及-CONR-之視情況選用之一個或多個連接部分,其中R選自氫及視情況經取代之C1至C10烷基;並且n係1至5之整數,通常係1。The first (matrix) polymer is aqueous alkali-soluble. The matrix polymer preferably includes a repeating unit having the general formula (I) and a repeating unit having the general formula (II): Wherein: R 1 independently represents H, halogen atom, C1-C3 alkyl or C1-C3 haloalkyl, usually H or methyl; R 2 represents optionally substituted straight chain, branched chain or cyclic C1- C20 alkyl, usually C1-C12 alkyl; L 1 represents a single bond or a polyvalent linking group, such as selected from the following: optionally substituted aliphatics such as C1-C6 alkylene and optionally Substituted aromatics such as C5-C20 aromatics and combinations thereof, and optionally one or more linking moieties selected from -O-, -S-, -COO-, and -CONR-, where R is selected from Hydrogen and optionally substituted C1 to C10 alkyl; and n is an integer from 1 to 5, usually 1.

咸信具有通式(I)之單元允許用於面塗層組合物中之溶劑中之基質聚合物具有良好的溶解度。由於其高度極性特性,具有通式(II)之單元可以賦予水性鹼顯影劑中之基質聚合物所期望的溶解度特徵。此允許光阻劑顯影期間的有效移除。The unit having the general formula (I) allows the matrix polymer in the solvent used in the topcoat composition to have good solubility. Due to its highly polar nature, units having the general formula (II) can impart desired solubility characteristics to the matrix polymer in the aqueous alkali developer. This allows effective removal during photoresist development.

具有通式(I)之單元在基質聚合物中之存在量以基質聚合物之總聚合單元計通常係10至90 mol%,通常50至80 mol%。具有通式(II)之單元在基質聚合物中之存在量以基質聚合物之總聚合單元計通常係10至90 mol%,通常20至50 mol%。The amount of the unit having the general formula (I) in the matrix polymer is usually 10 to 90 mol%, usually 50 to 80 mol% based on the total polymerized units of the matrix polymer. The amount of the unit having the general formula (II) in the matrix polymer is usually 10 to 90 mol%, usually 20 to 50 mol% based on the total polymerized units of the matrix polymer.

用於形成具有通式(I)之單元的例示性合適單體包含以下: Exemplary suitable monomers for forming units having general formula (I) include the following: .

用於形成具有通式(II)之單元的例示性合適單體包含以下: Exemplary suitable monomers for forming units having the general formula (II) include the following: .

基質聚合物可以另外或可替代地包括作為聚合單元的具有以下通式(III)之單體:其中R3 選自H、鹵素原子、C1-C3烷基或C1-C3鹵烷基;R4 獨立地選自經取代或未經取代之C1-C12烷基或經取代或未經取代之C5-C18芳基;X係C2-C6經取代或未經取代之伸烷基,通常係C2-C4並且更通常係C2經取代或未經取代之伸烷基;其中X可視情況包括一個或多個環以及R4 可視情況形成環;L2 係單鍵或連接基團,例如選自視情況經取代之伸烷基諸如C1-C6伸烷基及視情況經取代之伸芳基諸如C5-C20伸芳基以及其組合,及選自-O-、-S-、-COO-及-CONR-之視情況選用之一個或多個連接部分,其中選自氫及視情況經取代之C1至C10烷基;並且p係1至50之整數,通常係1至20、1至10或1;並且q係1至5之整數,通常係1至2或1。咸信具有通式(III)之單元允許面塗層組合物溶劑中之基質聚合物之良好溶解度,並可以賦予水性鹼顯影劑中之基質聚合物所期望的溶解度特徵。具有通式(III)之單元在基質聚合物中之存在量以基質聚合物之總聚合單元計可以係1至100 mol%,諸如10至70 mol%,15至60 mol%或20至50 mol%。The matrix polymer may additionally or alternatively include, as a polymerized unit, a monomer having the following general formula (III): Wherein R 3 is selected from H, halogen atom, C1-C3 alkyl or C1-C3 haloalkyl; R 4 is independently selected from substituted or unsubstituted C1-C12 alkyl or substituted or unsubstituted C5 -C18 aryl; X is C2-C6 substituted or unsubstituted alkylene, usually C2-C4 and more usually C2 substituted or unsubstituted alkylene; where X may optionally include one or more Each ring and R 4 may form a ring as appropriate; L 2 is a single bond or a linking group, for example, selected from optionally substituted alkylene such as C1-C6 alkylene and optionally substituted alkylene such as C5- C20 aryl and combinations thereof, and optionally one or more linking moieties selected from -O-, -S-, -COO-, and -CONR-, which are selected from hydrogen and optionally substituted C1 to C10 alkyl; and p is an integer of 1 to 50, usually 1 to 20, 1 to 10, or 1; and q is an integer of 1 to 5, usually 1 to 2 or 1. Xianxin has units of general formula (III) that allow good solubility of the matrix polymer in the solvent of the topcoat composition and can impart the desired solubility characteristics to the matrix polymer in the aqueous alkali developer. The amount of the unit having the general formula (III) in the matrix polymer may be 1 to 100 mol%, such as 10 to 70 mol%, 15 to 60 mol%, or 20 to 50 mol based on the total polymerized units of the matrix polymer. %.

基質聚合物可以包含如本文所描述之一種或多種額外類型之單元,例如含有磺醯胺基團(例如-NHSO2 CF3 )、氟烷基及/或氟醇基團(例如-C(CF3 )2 OH)之單元,從而用於增強聚合物之顯影劑溶解速率。若使用額外類型之單元,則其在基質聚合物中之存在量以基質聚合物之總聚合單元計通常係1至40 mol%。The matrix polymer may comprise one or more additional types of units as described herein, such as containing sulfonamide groups (eg, -NHSO 2 CF 3 ), fluoroalkyl, and / or fluoroalcohol groups (eg, -C (CF 3 ) 2 OH) units, thereby enhancing the developer dissolution rate of the polymer. If additional types of units are used, they are usually present in the matrix polymer in an amount of 1 to 40 mol% based on the total polymerized units of the matrix polymer.

基質聚合物應提供足夠高的顯影劑溶解速率以用於降低由於例如微橋接所致的整體缺陷率。用於基質聚合物之典型顯影劑溶解速率大於300奈米/秒,較佳大於1000奈米/秒並且更佳大於3000奈米/秒。The matrix polymer should provide a developer dissolution rate high enough to reduce the overall defect rate due to, for example, micro-bridges. A typical developer for a matrix polymer has a dissolution rate of greater than 300 nanometers / second, preferably greater than 1000 nanometers / second and more preferably greater than 3000 nanometers / second.

基質聚合物較佳具有高於表面活性聚合物表面能的表面能,並且較佳地基本上不可與表面活性聚合物混溶,從而使得表面活性聚合物與基質聚合物相分離並且遷移至遠離面塗層/光阻劑層界面的面塗層之上表面。基質聚合物之表面能通常係30至60 mN/m。The matrix polymer preferably has a surface energy higher than the surface energy of the surface-active polymer, and is preferably substantially immiscible with the surface-active polymer, so that the surface-active polymer is separated from the matrix polymer and migrates away from the surface The top surface of the topcoat at the coating / photoresist layer interface. The surface energy of the matrix polymer is usually 30 to 60 mN / m.

根據本發明之例示性基質聚合物包含以下: An exemplary matrix polymer according to the present invention includes the following: .

基質聚合物在所述組合物中之存在量以面塗層組合物之總固體計係70至99 wt%,通常85至95 wt%。基於聚苯乙烯標準物,基質聚合物之重均分子量Mw通常小於400,000,例如1000至50,000或2000至25,000。The matrix polymer is present in the composition in an amount of 70 to 99 wt%, usually 85 to 95 wt%, based on the total solids of the topcoat composition. Based on polystyrene standards, the weight average molecular weight Mw of the matrix polymer is usually less than 400,000, such as 1000 to 50,000 or 2000 to 25,000.

在浸沒式光微影製程之情況下,第二聚合物(表面活性聚合物)可以改進面塗層/浸沒流體界面處的表面特性。具體地說,第二聚合物可以提供關於水而言的所期望表面特性,例如面塗層/浸沒流體界面處的改進之靜態接觸角(SCA)、後退接觸角(RCA)、前進接觸角(ACA)以及滑動角(SA)中之一種或多種。具體地說,表面活性聚合物可以允許更高的RCA,此可以允許更快的掃描速度以及增加之處理吞吐量(process throughput)。呈乾燥狀態的面塗層組合物層的水後退接觸角通常係75至93°,並且較佳80至93°,並且更佳83至93°。短語「呈乾燥狀態」係指含有以全部面塗層組合物計8 wt%或更少之溶劑。In the case of an immersion photolithography process, a second polymer (surface-active polymer) can improve the surface characteristics at the topcoat / immersion fluid interface. Specifically, the second polymer can provide desired surface characteristics with respect to water, such as improved static contact angle (SCA), receding contact angle (RCA), advancing contact angle ( ACA) and sliding angle (SA). Specifically, surface-active polymers may allow for higher RCA, which may allow for faster scan speeds and increased process throughput. The water receding contact angle of the topcoat composition layer in the dry state is usually 75 to 93 °, and preferably 80 to 93 °, and more preferably 83 to 93 °. The phrase "in a dry state" refers to a solvent containing 8 wt% or less based on the entire top coating composition.

表面活性聚合物較佳係水性鹼溶性的以允許在用水性鹼顯影劑進行顯影期間的完全移除。表面活性聚合物較佳不含羧酸基團,因為此類基團可能降低聚合物之後退接觸角特性。The surface-active polymer is preferably aqueous alkali-soluble to allow complete removal during development with an aqueous alkaline developer. Surface-active polymers are preferably free of carboxylic acid groups, as such groups may reduce the polymer's receding contact angle characteristics.

表面活性聚合物應具有低於基質聚合物表面能的表面能。較佳地,表面活性聚合物具有顯著低於基質聚合物以及外塗層組合物中存在之其他聚合物表面能的表面能並且基本上不可與其混溶。面塗層組合物以此方式可以係自隔離的,其中在塗佈期間,通常在旋塗期間,表面活性聚合物遷移至遠離一種或多種其他聚合物之面塗層之上表面上。由此,在浸沒式光微影製程之情況下,在面塗層/浸沒流體界面處的面塗層上表面處,所得面塗層富含表面活性聚合物。富含表面活性聚合物之表面區域的厚度通常係一個至兩個單層或一個至三個單層,或厚度係約10至20 Å。雖然表面活性聚合物之所期望表面能將視特定基質聚合物及其表面能而定,但表面活性聚合物表面能通常係15至35 mN/m,較佳18至30 mN/m。表面活性聚合物通常比基質聚合物之彼等小5至25 mN/m,較佳比基質聚合物之彼等小5至15 mN/m。The surface-active polymer should have a surface energy that is lower than the surface energy of the matrix polymer. Preferably, the surface-active polymer has a surface energy that is significantly lower than and substantially immiscible with the surface energy of the matrix polymer and other polymers present in the overcoat composition. The topcoat composition can be self-isolating in this manner, wherein during coating, usually during spin coating, the surface-active polymer migrates to the top surface of the topcoat away from one or more other polymers. Thus, in the case of an immersion photolithography process, at the top surface of the top coating at the top coating / immersion fluid interface, the resulting top coating is rich in surface-active polymers. The surface area of the surface-rich polymer is usually one to two monolayers or one to three monolayers, or about 10 to 20 Å thick. Although the desired surface energy of the surface-active polymer will depend on the specific matrix polymer and its surface energy, the surface energy of the surface-active polymer is usually 15 to 35 mN / m, preferably 18 to 30 mN / m. Surface-active polymers are generally 5 to 25 mN / m smaller than those of the matrix polymer, preferably 5 to 15 mN / m smaller than those of the matrix polymer.

表面活性聚合物包括具有通式(IV)之重複單元及具有通式(V)之重複單元:其中:R5 獨立地表示H、鹵素原子、C1-C3烷基,通常H或甲基;R6 表示直鏈、分支鏈或環狀C1至C20氟烷基,通常C1至C12氟烷基;R7 表示直鏈、分支鏈或環狀C1至C20氟烷基,通常C1至C12氟烷基;L3 表示例如選自以下各項的多價連接基團:視情況經取代之脂族物諸如C1至C6伸烷基及視情況經取代之伸芳基諸如C5-C20伸芳基以及其組合,及選自-O-、-S-、-COO-及-CONR-之視情況選用之一個或多個連接部分,其中R選自氫及視情況經取代之C1至C10烷基,L3 較佳係-C(O)OCH2 -;並且n係1至5之整數,通常係1;其中第二聚合物不含非氟化側鏈;並且其中第二聚合物之存在量以所述組合物之總固體計係1至30 wt%。為清楚起見,通式(IV)及(V)中之R5 基團被認為係聚合物主鏈而不係側鏈的一部分。Surface-active polymers include repeating units having the general formula (IV) and repeating units having the general formula (V): Wherein: R 5 independently represents H, halogen atom, C1-C3 alkyl group, usually H or methyl; R 6 represents linear, branched or cyclic C1 to C20 fluoroalkyl group, usually C1 to C12 fluoroalkyl group; R 7 represents a linear, branched or cyclic C1 to C20 fluoroalkyl group, usually C1 to C12 fluoroalkyl group; L 3 represents a polyvalent linking group selected, for example, from the following: optionally substituted aliphatic Such as C1 to C6 alkylene and optionally substituted alkylene such as C5-C20 alkylene and combinations thereof, and optionally selected from -O-, -S-, -COO-, and -CONR- One or more linking moieties, wherein R is selected from hydrogen and optionally substituted C1 to C10 alkyl, L 3 is preferably -C (O) OCH 2- ; and n is an integer from 1 to 5, usually 1 ; Wherein the second polymer does not contain non-fluorinated side chains; and wherein the second polymer is present in an amount of 1 to 30 wt% based on the total solids of the composition. For clarity, the R 5 groups in the general formulae (IV) and (V) are considered to be part of the polymer main chain and not the side chains.

咸信由具有通式(IV)之單體形成之單元允許表面活性聚合物與所述組合物中之其他聚合物進行有效的相分離,增強之動態接觸角,例如增加之後退角及減小的滑動角。咸信由具有通式(V)之單體形成之單元有助於相分離及增強之動態接觸角特性以及賦予表面活性聚合物以有益的滯後特徵及改進之水性鹼顯影劑中溶解度。Units formed from monomers of general formula (IV) allow surface active polymers to be effectively phase separated from other polymers in the composition, enhancing dynamic contact angles, such as increasing receding angles and decreasing Sliding angle. Units formed from monomers having the general formula (V) contribute to phase separation and enhanced dynamic contact angle characteristics, as well as impart beneficial hysteresis characteristics to surface-active polymers and improved solubility in aqueous alkaline developers.

具有通式(IV)之單元在表面活性聚合物中之存在量以表面活性聚合物之總重複單元計通常係1至90 mol%,例如10至40 mol%。具有通式(IV)之單元在表面活性聚合物中之存在量以表面活性聚合物之總重複單元計通常係1至90 mol%,例如50至80 mol%。The amount of the unit having the general formula (IV) in the surface-active polymer is usually 1 to 90 mol%, such as 10 to 40 mol%, based on the total repeating units of the surface-active polymer. The amount of the unit having the general formula (IV) in the surface-active polymer is usually 1 to 90 mol%, such as 50 to 80 mol%, based on the total repeating units of the surface-active polymer.

用於具有通式(IV)之單元的例示性合適單體包含以下:Exemplary suitable monomers for units having the general formula (IV) include the following: .

用於具有通式(V)之單元的例示性合適單體包含以下:Exemplary suitable monomers for units having the general formula (V) include the following: .

表面活性聚合物可以包含一種或多種額外之單元類型。表面活性聚合物可以例如包含包括以下各項的一種或多種額外之單元:含氟側鏈基團,諸如氟化磺醯胺基、氟化醇基、氟化酯基、氟化側鏈上的酸不穩定離去基或其組合。含氟醇基之單元可以存在於表面活性聚合物中以達到增強顯影劑溶解度或允許增強之動態接觸角(例如增加之後退角及減小的滑動角)及改進顯影劑親和力及溶解度之目的。若使用額外類型之單元,則其在表面活性聚合物中之存在量以表面活性聚合物之總聚合單元計通常係1至70 mol%。Surface-active polymers may contain one or more additional unit types. The surface-active polymer may, for example, include one or more additional units including a fluorine-containing side chain group such as a fluorinated sulfonamide group, a fluorinated alcohol group, a fluorinated ester group, a fluorinated side chain Acid labile leaving groups or combinations thereof. The fluoroalcohol-based unit may be present in the surface-active polymer to achieve the purpose of enhancing the solubility of the developer or allowing an enhanced dynamic contact angle (such as an increased receding angle and a reduced sliding angle) and improving the developer affinity and solubility. If additional types of units are used, they are usually present in the surface-active polymer in an amount of 1 to 70 mol% based on the total polymerized units of the surface-active polymer.

適用作表面活性聚合物之例示性聚合物包含例如以下: 。 製造半導體裝置.Exemplary polymers suitable for use as surface-active polymers include, for example, the following: . Manufacturing of semiconductor devices.

用於浸沒式光微影的表面活性聚合物之含量下限值一般由防止光阻劑組分浸出的需要指定。表面活性聚合物在所述組合物中之存在量以面塗層組合物之總固體計通常係1至30 wt%,更通常3至20 wt%或5至15 wt%。表面活性聚合物之重均分子量通常小於400,000,較佳5000至50,000,更佳5000至25,000。The lower limit of the content of the surface-active polymer used for immersion photolithography is generally specified by the need to prevent the leaching of the photoresist component. The surface-active polymer is generally present in the composition in an amount of 1 to 30 wt%, more usually 3 to 20 wt% or 5 to 15 wt%, based on the total solids of the topcoat composition. The weight average molecular weight of the surface-active polymer is usually less than 400,000, preferably 5,000 to 50,000, and more preferably 5,000 to 25,000.

面塗層組合物中可以存在視情況選用之額外聚合物。舉例而言,除了基質聚合物及表面活性聚合物之外,亦可以提供添加劑聚合物以達到調整抗蝕劑特徵元件輪廓及/或控制抗蝕劑頂部缺失之目的。添加劑聚合物通常可與基質聚合物混溶並且基本上不可與表面活性聚合物混溶以使得表面活性聚合物可以遠離面塗層/光阻劑界面從其他聚合物中自隔離至面塗層表面上。Optionally, additional polymers may be present in the topcoat composition. For example, in addition to the matrix polymer and the surface-active polymer, an additive polymer may also be provided to achieve the purpose of adjusting the contour of the resist characteristic element and / or controlling the absence of the top of the resist. Additive polymers are generally miscible with the matrix polymer and are substantially immiscible with the surface-active polymer so that the surface-active polymer can self-isolate from other polymers to the surface of the topcoat away from the topcoat / photoresist interface on.

用於配製並且澆鑄面塗層組合物之典型溶劑材料係溶解或分散面塗層組合物之組分但不明顯地溶解底層光阻劑層的任何溶劑材料。總溶劑較佳係基於有機物的(亦即大於50 wt%有機物),通常90至100 wt%、更通常99至100 wt%或100 wt%有機溶劑,不包含殘留的水或其他污染物,其存在量以總溶劑計可以例如係0.05至1 wt%。不同溶劑例如兩種、三種或更多種溶劑之混合物較佳可以用於達成表面活性聚合物與所述組合物中之一種或多種其他聚合物隔離的有效相分離。溶劑混合物亦可以有效地降低配製物的黏度,此使得分配體積的減小。A typical solvent material used to formulate and cast the topcoat composition is any solvent material that dissolves or disperses the components of the topcoat composition but does not significantly dissolve the underlying photoresist layer. The total solvent is preferably organic-based (ie, greater than 50 wt% organics), typically 90 to 100 wt%, more usually 99 to 100 wt%, or 100 wt% organic solvents, and does not contain residual water or other contaminants, which The amount present may be, for example, from 0.05 to 1 wt% based on the total solvent. Different solvents, such as a mixture of two, three or more solvents, may preferably be used to achieve effective phase separation of the surface-active polymer from one or more other polymers in the composition. The solvent mixture can also effectively reduce the viscosity of the formulation, which results in a reduction in the dispensing volume.

在例示性態樣中,雙溶劑系統或三溶劑系統可以用於本發明之面塗層組合物。較佳之溶劑系統包含主要溶劑及附加溶劑並且可以包含較稀溶劑。關於面塗層組合物之非溶劑組分,主要溶劑通常展現出極佳的溶解特徵。雖然主要溶劑的所期望沸點將視溶劑系統之其他組分而定,但所述沸點通常小於附加溶劑的沸點,並且沸點典型地係120至140℃,諸如約130℃。合適的主要溶劑包含例如C4至C10單價醇,諸如正丁醇、異丁醇、2-甲基-1-丁醇、異戊醇、2,3-二甲基-1-丁醇、4-甲基-2-戊醇、異己醇、異庚醇、1-辛醇、1-壬醇及1-癸醇以及其混合物。主要溶劑之存在量以溶劑系統計通常係30至80 wt%。In an exemplary aspect, a two-solvent system or a three-solvent system can be used in the topcoat composition of the present invention. Preferred solvent systems include a primary solvent and an additional solvent and may include a more dilute solvent. With regard to the non-solvent component of the topcoat composition, the main solvent usually exhibits excellent dissolution characteristics. Although the desired boiling point of the primary solvent will depend on the other components of the solvent system, the boiling point is typically less than the boiling point of the additional solvent, and the boiling point is typically 120 to 140 ° C, such as about 130 ° C. Suitable main solvents include, for example, C4 to C10 monovalent alcohols such as n-butanol, isobutanol, 2-methyl-1-butanol, isoamyl alcohol, 2,3-dimethyl-1-butanol, 4- Methyl-2-pentanol, isohexanol, isoheptanol, 1-octanol, 1-nonanol and 1-decanol and mixtures thereof. The main solvent is usually present in an amount of 30 to 80 wt% based on the solvent system.

附加溶劑可以促進表面活性聚合物與面塗層組合物中之一種或多種其他聚合物之間的相分離以促進自隔離面塗層結構。另外,較高沸點的附加溶劑可以降低塗佈期間的末端乾燥效應。附加溶劑通常具有高於溶劑系統之其他組分沸點的沸點。雖然附加溶劑的所期望沸點將視溶劑系統之其他組分而定,但沸點通常係170至200℃,諸如約190℃。合適的附加溶劑包含例如羥基烷基醚,諸如具有下式之彼等羥基烷基醚: R11 -O-R12 -O-R13 -OH 其中R11 係視情況經取代之C1至C2烷基並且R12 及R13 獨立地選自視情況經取代之C2至C4烷基,並且此類羥基烷基醚之混合物包含異構體混合物。例示性羥基烷基醚包含二烷基二醇單烷基醚及其異構體,例如二乙二醇單甲醚、二丙二醇單甲醚、三丙二醇單甲醚、其異構體及其混合物。附加溶劑之存在量以溶劑系統計通常係3至15 wt%。The additional solvent may promote phase separation between the surface-active polymer and one or more other polymers in the topcoat composition to promote a self-isolating topcoat structure. In addition, higher boiling point additional solvents can reduce the end-drying effect during coating. The additional solvent usually has a boiling point higher than the boiling points of other components of the solvent system. Although the desired boiling point of the additional solvent will depend on the other components of the solvent system, the boiling point is usually 170 to 200 ° C, such as about 190 ° C. Suitable additional solvents include, for example, hydroxyalkyl ethers, such as their hydroxyalkyl ethers having the formula: R 11 -OR 12 -OR 13 -OH where R 11 is optionally substituted C1 to C2 alkyl and R 12 And R 13 are independently selected from optionally substituted C2 to C4 alkyl, and a mixture of such hydroxyalkyl ethers comprises a mixture of isomers. Exemplary hydroxyalkyl ethers include dialkyl glycol monoalkyl ethers and isomers thereof, such as diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, isomers thereof, and mixtures thereof . The amount of additional solvent present is usually 3 to 15 wt% based on the solvent system.

較稀溶劑可用於降低黏度並在較低的分配體積下改進塗層覆蓋率。較稀溶劑通常係用於相對於主要溶劑的所述組合物之非溶劑組分的較貧溶劑。雖然較稀溶劑的所期望沸點將視溶劑系統之其他組分而定,但沸點典型係140至180℃,諸如約170℃。合適的較稀溶劑包含例如烷烴,諸如C8至C12正烷烴,例如正辛烷、正癸烷及十二烷、其異構體以及其異構體之混合物;及/或烷基醚,諸如具有式R14 -O-R15 之彼等烷基醚,其中R14 及R15 獨立地選自C2至C8烷基、C2至C6烷基及C2至C4烷基。烷基醚基團可以係直鏈或分支鏈的及對稱的或不對稱的。特別合適的烷基醚包含例如異丁基醚、異戊基醚、異丁基異己基醚及其混合物。其他合適的較稀溶劑包含酯溶劑,例如由通式(VII)表示之彼等酯溶劑:其中:R16 及R17 獨立地選自C3至C8烷基;並且合起來的R16 及R17 中之碳原子總數大於6。合適的此類酯溶劑包含例如戊酸丙酯、戊酸異丙酯、3-甲基丁酸異丙酯、2-甲基丁酸異丙酯、特戊酸異丙酯、異丁酸異丁酯、異丁酸2-甲基丁酯、2-甲基丁酸2-甲基丁酯、2-甲基己酸2-甲基丁酯、庚酸2-甲基丁酯、庚酸己酯、正丁酸正丁酯、正丁酸異戊酯及異戊酸異戊酯。若使用較稀溶劑,則其存在量以溶劑系統計通常係10至70 wt%。Dilute solvents can be used to reduce viscosity and improve coating coverage at lower dispensing volumes. Leaner solvents are generally leaner solvents for the non-solvent components of the composition relative to the primary solvent. Although the desired boiling point of the dilute solvent will depend on the other components of the solvent system, the boiling point is typically 140 to 180 ° C, such as about 170 ° C. Suitable dilute solvents include, for example, alkanes, such as C8 to C12 n-alkanes, such as n-octane, n-decane, and dodecane, their isomers, and mixtures of isomers thereof; and / or alkyl ethers such as those having Their alkyl ethers of formula R 14 -OR 15 wherein R 14 and R 15 are independently selected from C2 to C8 alkyl, C2 to C6 alkyl and C2 to C4 alkyl. Alkyl ether groups can be straight or branched and symmetric or asymmetric. Particularly suitable alkyl ethers include, for example, isobutyl ether, isoamyl ether, isobutyl isohexyl ether, and mixtures thereof. Other suitable dilute solvents include ester solvents, such as their ester solvents represented by the general formula (VII): Wherein: R 16 and R 17 are independently selected from C3 to C8 alkyl groups; and the total number of carbon atoms in R 16 and R 17 combined is greater than 6. Suitable such ester solvents include, for example, propyl valerate, isopropyl valerate, isopropyl 3-methylbutyrate, isopropyl 2-methylbutyrate, isopropyl pivalate, isobutyrate Butyl ester, 2-methylbutyl isobutyrate, 2-methylbutyl 2-methylbutanoate, 2-methylbutyl 2-hexanoate, 2-methylbutyl heptanoate, heptanoic acid Hexyl ester, n-butyl n-butyrate, iso-amyl n-butyrate and iso-amyl isovalerate. If a dilute solvent is used, it is usually present in an amount of 10 to 70 wt% based on the solvent system.

特別較佳之溶劑系統包含4-甲基-2-戊醇、二丙二醇甲醚及異丁酸異丁酯。雖然已經關於兩組分系統及三組分系統描述了例示性溶劑系統,但應該清楚,可以使用額外之溶劑。舉例而言,可以採用一種或多種額外的主要溶劑、較稀溶劑、附加溶劑及/或其他溶劑。Particularly preferred solvent systems include 4-methyl-2-pentanol, dipropylene glycol methyl ether, and isobutyl isobutyrate. Although exemplary solvent systems have been described with respect to two-component and three-component systems, it should be clear that additional solvents may be used. For example, one or more additional primary solvents, dilute solvents, additional solvents, and / or other solvents may be used.

面塗層組合物可以包括一種或多種其他視情況選用之組分。舉例而言,所述組合物可以包含用於增強抗反射特性的光化染料及對比染料、抗條紋劑等中之一種或多種。若使用此類視情況選用之添加劑,則其以外塗層組合物之總固體計通常以微量諸如0.1至10 wt%存在於所述組合物中。The topcoat composition may include one or more other optional components. For example, the composition may include one or more of a photochemical dye and a contrast dye, an anti-stripe agent, and the like for enhancing anti-reflection characteristics. If such optional additives are used, the total solids of the outer coating composition is usually present in the composition in a trace amount such as 0.1 to 10 wt%.

面塗層組合物中包含酸生成劑化合物諸如光酸生成劑(PAG)及/或熱酸生成劑(TAG)化合物可以係有益的。合適的光酸生成劑在化學增幅型光阻劑領域中係已知的,並且包含例如:鎓鹽,例如三氟甲烷磺酸三苯基鋶、三氟甲烷磺酸(對第三丁氧基苯基)二苯基鋶、三氟甲烷磺酸三(對第三丁氧基苯基)鋶、對甲苯磺酸三苯基鋶;硝基苄基衍生物,例如2-硝基苄基-對甲苯磺酸鹽、2,6-二硝基苄基-對甲苯磺酸鹽及2,4-二硝基苄基-對甲苯磺酸鹽;磺酸酯,例如1,2,3-三(甲烷磺醯基氧基)苯、1,2,3-三(三氟甲烷磺醯基氧基)苯及1,2,3-三(對甲苯磺醯基氧基)苯;重氮甲烷衍生物,例如雙(苯磺醯基)重氮甲烷、雙(對甲苯磺醯基)重氮甲烷;乙二肟衍生物,例如雙-O-(對甲苯磺醯基)-α-二甲基乙二肟及雙-O-(正丁烷磺醯基)-α-二甲基乙二肟;N-羥基醯亞胺化合物的磺酸酯衍生物,例如N-羥基丁二醯亞胺甲磺酸酯、N-羥基丁二醯亞胺三氟甲磺酸酯;及含鹵素的三嗪化合物,例如2-(4-甲氧基苯基)-4,6-雙(三氯甲基)-1,3,5-三嗪及2-(4-甲氧基萘基)-4,6-雙(三氯甲基)-1,3,5-三嗪。可以使用此類PAG中之一種或多種。It may be beneficial to include an acid generator compound such as a photoacid generator (PAG) and / or a thermal acid generator (TAG) compound in the topcoat composition. Suitable photoacid generators are known in the field of chemically amplified photoresists and include, for example, onium salts such as triphenylphosphonium trifluoromethanesulfonate, trifluoromethanesulfonic acid (p-third butoxy Phenyl) diphenylphosphonium, tris (p-third-butoxyphenyl) phosphonium trifluoromethanesulfonate, triphenylphosphonium p-toluenesulfonic acid; nitrobenzyl derivatives, such as 2-nitrobenzyl- P-toluenesulfonate, 2,6-dinitrobenzyl-p-toluenesulfonate and 2,4-dinitrobenzyl-p-toluenesulfonate; sulfonates such as 1,2,3-tris (Methanesulfonyloxy) benzene, 1,2,3-tris (trifluoromethanesulfonyloxy) benzene and 1,2,3-tris (p-toluenesulfonyloxy) benzene; diazomethane Derivatives, such as bis (benzenesulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane; ethylenedioxime derivatives, such as bis-O- (p-toluenesulfonyl) -α-dimethyl Ethylenedioxime and bis-O- (n-butanesulfonamido) -α-dimethylethylenedioxime; sulfonate derivatives of N-hydroxyfluorimide compounds, such as N-hydroxysuccinimide Mesylate, N-hydroxysuccinimide trifluoromethanesulfonate; and halogen-containing triazine compounds, such as 2- (4-methoxybenzene ) -4,6-bis (trichloromethyl) -1,3,5-triazine and 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -1,3 , 5-triazine. One or more of such PAGs can be used.

合適的熱酸生成劑包括例如甲苯磺酸硝基苄酯,諸如甲苯磺酸2-硝基苄酯、甲苯磺酸2,4-二硝基苄酯、甲苯磺酸2,6-二硝基苄酯、甲苯磺酸4-硝基苄酯;苯磺酸酯,諸如4-氯苯磺酸2-三氟甲基-6-硝基苄酯、苯磺酸2-三氟甲基-6-硝基苄基4-硝酯;酚醛磺酸酯,諸如4-甲氧基苯磺酸苯酯;有機酸之烷基銨鹽,諸如10-樟腦磺酸、三氟甲基苯磺酸、全氟丁烷磺酸之三乙銨鹽;及特定鎓鹽。各種芳族(蒽、萘或苯衍生物)磺酸胺鹽可以用作TAG,包含美國專利第第3,474,054號、第4,200,729號、第4.251,665號及第5,187,019號中所揭示之彼等鹽。TAG之實例包含由美國康涅狄格州諾沃克的King Industries以NACURE™、CDX™及K-PURE™名稱例如NACURE 5225、CDX-2168E、K-PURE™2678及K-PURE™2700出售之彼等TAG。可以使用此類TAG中之一種或多種。Suitable thermal acid generators include, for example, nitrobenzyl tosylate, such as 2-nitrobenzyl tosylate, 2,4-dinitrobenzyl tosylate, 2,6-dinitrotosylate Benzyl ester, 4-nitrobenzyl tosylate; benzenesulfonates such as 2-trifluoromethyl-6-nitrobenzyl 4-chlorobenzenesulfonate, 2-trifluoromethyl-6 benzenesulfonate -Nitrobenzyl 4-nitroester; phenol sulfonates such as phenyl 4-methoxybenzenesulfonate; alkylammonium salts of organic acids such as 10-camphorsulfonic acid, trifluoromethylbenzenesulfonic acid, Triethylammonium salt of perfluorobutanesulfonic acid; and specific onium salts. Various aromatic (anthracene, naphthalene, or benzene derivative) sulfonate amine salts can be used as TAGs, including those disclosed in US Patent Nos. 3,474,054, 4,200,729, 4.251,665, and 5,187,019. Examples of TAGs include those TAGs sold by King Industries, Norwalk, Connecticut, USA under the names NACURE ™, CDX ™ and K-PURE ™ such as NACURE 5225, CDX-2168E, K-PURE ™ 2678 and K-PURE ™ 2700. One or more of such TAGs can be used.

若採用一種或多種酸生成劑,則其可以以相對較少量例如以所述組合物之總固體計0.1至8 wt%用於面塗層組合物中。一種或多種酸生成劑化合物的此種使用可以有利地影響在底層抗蝕劑層中圖案化的顯影影像的光微影效能,特別係解析率。If one or more acid generators are used, they can be used in the topcoat composition in relatively small amounts, for example, from 0.1 to 8 wt% based on the total solids of the composition. Such use of one or more acid generator compounds can favorably affect the photolithographic performance of the developed image patterned in the underlying resist layer, especially resolution.

由所述組合物形成之面塗層之折射率通常在193 nm下係1.4或更大,較佳在193 nm下係1.47或更大。折射率可以藉由改變基質聚合物、表面活性聚合物、添加劑聚合物或外塗層組合物之其他組分的組成來調整。舉例而言,增加外塗層組合物中之有機內容物的相對量可以提供層的增加之折射率。較佳的外塗層組合物層在目標暴露波長下之折射率在浸沒流體之折射率與光阻劑之折射率之間。The refractive index of the top coat formed from the composition is usually 1.4 or more at 193 nm, and preferably 1.47 or more at 193 nm. The refractive index can be adjusted by changing the composition of the matrix polymer, surface-active polymer, additive polymer, or other components of the overcoat composition. For example, increasing the relative amount of organic content in the overcoat composition can provide an increased refractive index of the layer. The refractive index of the preferred outer coating composition layer at the target exposure wavelength is between the refractive index of the immersion fluid and the refractive index of the photoresist.

光阻劑面塗層組合物可以遵照已知程序來製備。舉例而言,所述組合物可以藉由將所述組合物之固體組分溶解於溶劑組分中來製備。所述組合物之所期望總固體含量將視諸如所述組合物中之特定聚合物及所期望最終層厚度的因素而定。外塗層組合物之固體含量以所述組合物之總重量計較佳係1至10 wt%,更佳1至5 wt%。全部組合物之黏度通常係1.5至2厘泊(cp)。光阻劑 The photoresist topcoat composition can be prepared according to known procedures. For example, the composition can be prepared by dissolving the solid component of the composition in a solvent component. The desired total solids content of the composition will depend on factors such as the particular polymer in the composition and the desired final layer thickness. The solid content of the overcoat composition is preferably 1 to 10 wt%, more preferably 1 to 5 wt%, based on the total weight of the composition. The viscosity of the entire composition is usually 1.5 to 2 centipoise (cp). Photoresist

適用於本發明之光阻劑組合物包含包括酸敏感性基質聚合物之化學增幅型光阻劑組合物,意味著作為光阻劑組合物層的一部分,聚合物及組合物層經歷顯影劑中溶解度的變化,此係因為其與由光酸生成劑生成的酸進行反應,隨後進行軟烘烤,暴露於活化輻射及暴露後烘烤。抗蝕劑配製物可以係正作用的或負作用的,但通常係正作用的。在正型光阻劑中,溶解度變化通常發生在基質聚合物中之酸不穩定基團諸如光酸不穩定酯或縮醛基在暴露於活化輻射及熱處理時經歷光酸促進的去保護反應之時。適用於本發明之合適之光阻劑組合物係市售的。A photoresist composition suitable for use in the present invention includes a chemically amplified photoresist composition including an acid-sensitive matrix polymer, meaning that the work is part of a photoresist composition layer, and the polymer and composition layer are subjected to a developer The change in solubility is due to its reaction with the acid generated by the photoacid generator, followed by soft baking, exposure to activating radiation and baking after exposure. Resist formulations can be positive or negative, but are usually positive. In positive photoresists, solubility changes usually occur in acid-labile groups such as photoacid-labile esters or acetal groups in matrix polymers that undergo photoacid-promoted deprotection reactions when exposed to activating radiation and heat treatment Time. Suitable photoresist compositions suitable for use in the present invention are commercially available.

對於在諸如193 nm的波長下的成像,基質聚合物通常基本上不含(例如小於15莫耳%)或完全不含苯基、苄基或其他芳族基團,其中此類基團高度吸收輻射。歐洲申請EP930542A1及美國專利第第6,692,888號及第6,680,159號中揭示了基本上不含或完全不含芳族基團的合適之聚合物,其全部都係Shipley Company的。較佳的酸不穩定基團包含例如含有共價連接至基質聚合物之酯的羧基氧的第三非環烷基碳(例如第三丁基)或第三脂環族碳(例如甲基金剛烷基)的縮醛基或酯基。For imaging at wavelengths such as 193 nm, the matrix polymer is generally substantially free (eg, less than 15 mole%) or completely free of phenyl, benzyl, or other aromatic groups, where such groups are highly absorbent radiation. European applications EP930542A1 and U.S. Patent Nos. 6,692,888 and 6,680,159 disclose suitable polymers that are substantially free or completely free of aromatic groups, all of which are of the Shipley Company. Preferred acid labile groups include, for example, a third non-cycloalkyl carbon (such as a third butyl) or a third alicyclic carbon (such as methyladamantine) containing a carboxyl oxygen covalently attached to the ester of the matrix polymer. Alkyl) acetal or ester.

合適的基質聚合物進一步包含含有(烷基)丙烯酸酯單元之聚合物,較佳包含酸不穩定的(烷基)丙烯酸酯單元,諸如丙烯酸第三丁酯、甲基丙烯酸第三丁酯、丙烯酸甲基金剛烷酯、甲基丙烯酸甲基金剛烷酯、丙烯酸乙基小茴香酯、甲基丙烯酸乙基小茴香酯等以及其他非環烷基及脂環族(烷基)丙烯酸酯。例如美國專利。第6,057,083號、歐洲公開申請案EP01008913A1及EP00930542A1以及美國專利第6,136,501號中描述了此類聚合物。其他合適的基質聚合物包含例如彼等含有非芳族環烯烴(內環雙鍵)之聚合單元的基質聚合物,諸如視情況經取代之降冰片烯,例如美國專利第5,843,624號及第6,048,664號中描述了聚合物。再其他合適的基質聚合物包含含有聚合酐單元、特別地聚合順丁烯二酸酐及/或衣康酸酐單元之聚合物,諸如揭示於歐洲公開申請案EP01008913A1及美國專利第6,048,662號中。Suitable matrix polymers further comprise polymers containing (alkyl) acrylate units, preferably acid-labile (alkyl) acrylate units, such as third butyl acrylate, third butyl methacrylate, acrylic acid Methyladamantyl ester, methyladamantyl methacrylate, ethyl cumin acrylate, ethyl cumin methacrylate, etc. and other non-cycloalkyl and alicyclic (alkyl) acrylates. For example, US patents. Such polymers are described in No. 6,057,083, European Published Applications EP01008913A1 and EP00930542A1, and US Patent No. 6,136,501. Other suitable matrix polymers include, for example, their matrix polymers containing polymerized units of non-aromatic cyclic olefins (internal ring double bonds), such as optionally substituted norbornene, such as US Patent Nos. 5,843,624 and 6,048,664 Polymers are described in. Yet other suitable matrix polymers include polymers containing polymerized anhydride units, particularly polymerized maleic anhydride and / or itaconic anhydride units, such as disclosed in European Published Application EP01008913A1 and US Patent No. 6,048,662.

亦適用作基質聚合物之係含有含雜原子、特別地氧及/或硫之重複單元(但酸酐除外,亦即所述單元不含酮環原子)之樹脂。雜脂環單元可以稠合至聚合物主鏈,並且可以包括諸如利用聚合降冰片烯基團得到之稠合碳脂環單元及/或諸如利用聚合順丁烯二酸酐或衣康酸酐得到之酸酐單元。PCT/US01/14914及美國專利第6,306,554號中揭示了此類聚合物。其他合適的含雜原子基團的基質聚合物包含含有經一個或多個含雜原子(例如氧或硫)之基團例如羥基萘基取代之聚合碳環芳基單元之聚合物,諸如揭示於美國專利第7,244,542號中。Also suitable as a matrix polymer are resins containing repeating units containing heteroatoms, particularly oxygen and / or sulfur (except for anhydrides, that is to say the units do not contain keto ring atoms). Heteroalicyclic units may be fused to the polymer backbone and may include fused carbocyclic units such as obtained by polymerizing norbornene groups and / or acid anhydrides such as obtained by polymerizing maleic anhydride or itaconic anhydride unit. Such polymers are disclosed in PCT / US01 / 14914 and US Patent No. 6,306,554. Other suitable heteroatom-containing matrix polymers include polymers containing polymeric carbocyclic aryl units substituted with one or more heteroatom-containing (such as oxygen or sulfur) groups, such as hydroxynaphthyl, such as disclosed in U.S. Patent No. 7,244,542.

上述基質聚合物中之兩種或更多種之摻合物可以適當地用於光阻劑組合物中。Blends of two or more of the above-mentioned matrix polymers can be suitably used in the photoresist composition.

用於光阻劑組合物中之合適的基質聚合物係市售的,並且可由本領域中熟習此項技術者容易地製備。基質聚合物以足以使抗蝕劑的暴露塗層可在合適的顯影劑溶液中顯影之量存在於抗蝕劑組合物中。基質聚合物在所述組合物中之存在量以抗蝕劑組合物之總固體計通常係50至95 wt%。基質聚合物之重均分子量Mw 通常小於100,000,例如5000至100,000,更通常5000至15,000。Suitable matrix polymers for use in photoresist compositions are commercially available and can be easily prepared by those skilled in the art. The matrix polymer is present in the resist composition in an amount sufficient that the exposed coating of the resist can be developed in a suitable developer solution. The matrix polymer is typically present in the composition in an amount of 50 to 95 wt% based on the total solids of the resist composition. The weight average molecular weight Mw of the matrix polymer is usually less than 100,000, such as 5000 to 100,000, and more usually 5000 to 15,000.

光阻劑組合物進一步包括光活性組分,諸如以足以在暴露於活化輻射後在所述組合物之塗層中產生潛像之量採用的光酸生成劑(PAG)。舉例而言,光酸生成劑之存在量以光阻劑組合物之總固體計應適當地係約1至20 wt%。通常,與非化學增幅型材料相比,較少量的PAG適用於化學增幅型抗蝕劑。合適的PAG在化學增幅型光阻劑領域中係已知的,並且包含例如以上關於面塗層組合物所描述之彼等物質。The photoresist composition further includes a photoactive component such as a photoacid generator (PAG) employed in an amount sufficient to produce a latent image in a coating of the composition upon exposure to activating radiation. For example, the photoacid generator is suitably present in an amount of about 1 to 20 wt% based on the total solids of the photoresist composition. Generally, a smaller amount of PAG is suitable for chemically amplified resists than non-chemically amplified materials. Suitable PAGs are known in the field of chemically amplified photoresists and include, for example, those described above with respect to the topcoat composition.

適用於光阻劑組合物之溶劑包含例如:二醇醚,諸如2-甲氧基乙醚(二乙二醇二甲醚)、乙二醇單甲醚及丙二醇單甲醚;丙二醇單甲醚乙酸酯;乳酸酯,諸如乳酸甲酯及乳酸乙酯;丙酸酯,諸如丙酸甲酯、丙酸乙酯、乙基乙氧基丙酸酯及異丁酸甲基-2-羥酯;溶纖劑酯,諸如甲基溶纖劑乙酸酯;芳族烴,諸如甲苯及二甲苯;及酮,諸如丙酮、甲基乙基酮、環己酮及2-庚酮。溶劑之摻合物,諸如以上所描述之溶劑中之兩種、三種或更多種之摻合物亦係合適的。溶劑在所述組合物中之存在量以光阻劑組合物之總重量計通常係90至99 wt%,更通常95至98 wt%。Suitable solvents for the photoresist composition include, for example: glycol ethers such as 2-methoxyethyl ether (diethylene glycol dimethyl ether), ethylene glycol monomethyl ether and propylene glycol monomethyl ether; propylene glycol monomethyl ether ethyl Esters; lactates such as methyl lactate and ethyl lactate; propionates such as methyl propionate, ethyl propionate, ethyl ethoxypropionate, and methyl-2-hydroxy isobutyrate ; Cellosolve esters such as methyl cellosolve acetate; aromatic hydrocarbons such as toluene and xylene; and ketones such as acetone, methyl ethyl ketone, cyclohexanone, and 2-heptanone. Blends of solvents such as blends of two, three or more of the solvents described above are also suitable. The solvent is generally present in the composition in an amount of 90 to 99 wt%, more usually 95 to 98 wt%, based on the total weight of the photoresist composition.

光阻劑組合物亦可以包含其他視情況選用之材料。舉例而言,所述組合物可以包含光化染料及對比染料、抗條紋劑、塑化劑、增速劑、敏化劑等中之一種或多種。若使用此類視情況選用之添加劑,則其通常以光阻劑組合物之總固體計以微量諸如0.1至10 wt%存在於所述組合物中。The photoresist composition may also include other optional materials. For example, the composition may include one or more of a photochemical dye and a contrast dye, an anti-stripe agent, a plasticizer, a speed increasing agent, a sensitizer, and the like. If such an optional additive is used, it is usually present in the composition in a trace amount such as 0.1 to 10 wt% based on the total solids of the photoresist composition.

抗蝕劑組合物之較佳的視情況選用之添加劑係添加的鹼。合適的鹼係本領域中已知的並且包括例如直鏈及環狀醯胺及其衍生物,諸如N,N-雙(2-羥乙基)特戊醯胺、N,N-二乙基乙醯胺、N1,N1,N3,N3-四丁基丙二醯胺、1-甲基氮雜環庚烷-2-酮、1-烯丙基氮雜環庚烷-2-酮及1,3-二羥基-2-(羥甲基)丙醯-2-基胺基甲酸第三丁酯;芳族胺,諸如吡啶及二第三丁基吡啶;脂族胺,諸如三異丙醇胺、正第三丁基二乙醇胺、雙(2-乙醯氧基-乙基)胺、2,2',2'',2'''-(乙烷-1,2-二基雙(氮烷三基))四乙醇及2-(二丁胺基)乙醇、2,2',2''-氮基三乙醇;環狀脂族胺,諸如1-(第三丁氧基羰基)-4-羥基哌啶、1-吡咯啶羧酸第三丁酯、2-乙基-1H-咪唑-1-羧酸第三丁酯、哌嗪-1,4-二羧酸二第三丁酯及N(2-乙醯氧基-乙基)嗎啉。添加的鹼適當地以相對較小之量例如以光阻劑組合物之總固體計0.01至5 wt%、較佳0.1至2 wt%使用。The preferred optional additives for the resist composition are added alkalis. Suitable bases are known in the art and include, for example, linear and cyclic amidines and derivatives thereof, such as N, N-bis (2-hydroxyethyl) pentamidine, N, N-diethyl Ethylamine, N1, N1, N3, N3-tetrabutylpropanediamine, 1-methylazacycloheptan-2-one, 1-allylazepan-2-one and 1 3,3-Dihydroxy-2- (hydroxymethyl) propan-2-ylaminocarboxylic acid tert-butyl ester; aromatic amines such as pyridine and di-tert-butylpyridine; aliphatic amines such as triisopropanol Amine, n-tert-butyldiethanolamine, bis (2-ethoxymethyl-ethyl) amine, 2,2 ', 2' ', 2' ''-(ethane-1,2-diylbis ( Azaalkanetriyl)) tetraethanol and 2- (dibutylamino) ethanol, 2,2 ', 2' '-nitrotriethanol; cyclic aliphatic amines such as 1- (third butoxycarbonyl) 4-Hydroxypiperidine, 1-pyrrolidinecarboxylic acid tert-butyl ester, 2-ethyl-1H-imidazole-1-carboxylic acid tert-butyl ester, piperazine-1,4-dicarboxylic acid tert-butyl ester Esters and N (2-acetamido-ethyl) morpholine. The added base is suitably used in a relatively small amount, for example, from 0.01 to 5 wt%, preferably from 0.1 to 2 wt%, based on the total solids of the photoresist composition.

光阻劑可以遵照已知程序來製備。舉例而言,可以藉由將光阻劑的固體組分溶解於溶劑組分中來將抗蝕劑製備為塗層組合物。光阻劑的所期望總固體含量將視諸如所述組合物中之特定聚合物、最終層厚度及暴露波長的因素而定。光阻劑的固體含量以光阻劑組合物之總重量計通常在1至10 wt%、更通常2至5 wt%之間變化。光微影處理 Photoresist can be prepared according to known procedures. For example, a resist can be prepared as a coating composition by dissolving a solid component of a photoresist in a solvent component. The desired total solids content of the photoresist will depend on factors such as the particular polymer in the composition, the final layer thickness, and the exposure wavelength. The solids content of the photoresist typically varies between 1 and 10 wt%, more usually between 2 and 5 wt%, based on the total weight of the photoresist composition. Photolithography

液體光阻劑組合物可以藉由諸如旋塗、浸漬、滾塗或其他習知的塗佈技術並且通常為旋塗來施用於基板。當旋塗時,塗料溶液的固體含量可以基於所利用的特定旋轉設備、溶液黏度、旋轉器速度以及允許旋轉的時間量來進行調節以得到所期望的膜厚度。The liquid photoresist composition can be applied to a substrate by, for example, spin coating, dipping, roll coating, or other well-known coating techniques and is usually spin coating. When spin coating, the solids content of the coating solution can be adjusted based on the particular rotating equipment utilized, solution viscosity, spinner speed, and amount of time allowed to rotate to obtain the desired film thickness.

用於本發明方法之光阻劑組合物以用於施用光阻劑的習知方式適當地施用於基板。舉例而言,可以將所述組合物施用於矽晶圓或塗佈有一個或多個層並且具有表面特徵元件的矽晶圓上以產生微處理器或其他積體電路組件。亦可以適當地採用鋁-氧化鋁、砷化鎵、陶瓷、石英、銅、玻璃基板等。光阻劑組合物通常施用於抗反射層例如有機抗反射層上。The photoresist composition used in the method of the present invention is suitably applied to a substrate in a conventional manner for applying photoresist. For example, the composition can be applied to a silicon wafer or a silicon wafer coated with one or more layers and having surface features to produce a microprocessor or other integrated circuit component. Aluminium-alumina, gallium arsenide, ceramics, quartz, copper, glass substrates, and the like can also be appropriately used. The photoresist composition is usually applied to an anti-reflection layer such as an organic anti-reflection layer.

本發明之面塗層組合物可以藉由諸如以上參考光阻劑組合物所描述之任何合適之方法並且通常係旋塗來施用於光阻劑組合物上。The topcoat composition of the present invention can be applied to the photoresist composition by any suitable method such as described above with reference to the photoresist composition and is usually spin-coated.

在將光阻劑塗佈至表面上之後,可以將其加熱(軟烘烤)以移除溶劑直至通常光阻劑塗層係無黏性的,或可以在施用面塗層組合物之後乾燥光阻劑層並且在單一熱處理步驟中將來自光阻劑組合物層及面塗層組合物層之溶劑基本上移除。After the photoresist is applied to the surface, it may be heated (soft baked) to remove the solvent until the photoresist coating is generally non-sticky, or the photoresist may be dried after application of the topcoat composition. The resist layer and the solvent from the photoresist composition layer and the top coating composition layer are substantially removed in a single heat treatment step.

接著使具有外塗佈面塗層之光阻劑層經由圖案化光遮罩暴露以針對光阻劑的光活性組分活化的輻射。暴露通常在浸沒式掃描儀情況下進行,但可替代地可以在乾燥(非浸沒)暴露工具情況下進行。The photoresist layer with an overcoat topcoat is then exposed via a patterned photomask to radiation that is activated against the photoactive component of the photoresist. Exposure is usually performed with an immersion scanner, but may alternatively be performed with a dry (non-immersion) exposure tool.

在暴露步驟期間,光阻劑組合物層暴露於圖案化活化輻射,並且視暴露工具及光阻劑組合物之組分而定暴露能通常在約1至100 mJ/cm2 範圍內。本文對將光阻劑組合物暴露於針對光阻劑活化的輻射的提及表明輻射能夠在光阻劑中形成潛像,諸如藉由引起光活性組分的反應進行,例如由光酸生成劑化合物產生光酸。During the exposure step, the photoresist composition layer is exposed to patterned activating radiation, and the exposure energy is usually in the range of about 1 to 100 mJ / cm 2 depending on the components of the exposure tool and the photoresist composition. Reference herein to the exposure of a photoresist composition to radiation directed against photoresist activation indicates that radiation can form a latent image in the photoresist, such as by causing a reaction of a photoactive component, such as by a photoacid generator The compound produces photoacid.

光阻劑組合物(及在光敏性時面塗層組合物)通常藉由短暴露波長來光活化,例如波長小於300 nm諸如248 nm、193 nm及EUV波長諸如13.5 nm的輻射。暴露之後,通常在約70℃至約160℃範圍內的溫度下烘烤所述組合物層。Photoresist compositions (and topcoat compositions when photosensitive) are typically photoactivated by short exposure wavelengths, such as radiation with wavelengths less than 300 nm such as 248 nm, 193 nm, and EUV wavelengths such as 13.5 nm. After exposure, the composition layer is typically baked at a temperature in the range of about 70 ° C to about 160 ° C.

此後,使膜顯影,通常藉由用例如選自以下各項的水性鹼顯影劑處理:氫氧化四級銨溶液,諸如氫氧化四烷基銨溶液,通常0.26 N氫氧化四甲基銨;胺溶液,諸如乙胺、正丙胺、二乙胺、二正丙胺、三乙胺或甲基二乙胺;醇胺,諸如二乙醇胺或三乙醇胺;及環胺,諸如吡咯或吡啶。一般來說,顯影依照本領域所公認的程序。Thereafter, the film is developed, usually by treatment with, for example, an aqueous alkali developer selected from the group consisting of a quaternary ammonium hydroxide solution, such as a tetraalkylammonium hydroxide solution, typically 0.26 N tetramethylammonium hydroxide; an amine Solutions such as ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine or methyldiethylamine; alcoholamines such as diethanolamine or triethanolamine; and cyclic amines such as pyrrole or pyridine. Generally, development follows procedures recognized in the art.

在光阻劑層顯影之後,可以例如根據本領域中已知的程序藉由化學蝕刻或鍍覆缺乏抗蝕劑的基板區域,在缺乏抗蝕劑之彼等區域上對經顯影基板進行選擇性處理。在此類處理之後,可以使用已知剝離程序移除基板上剩餘的抗蝕劑。After the photoresist layer is developed, the developed substrate may be selectively selected on those areas lacking the resist by chemical etching or plating the areas lacking the resist, for example, according to procedures known in the art. deal with. After such processing, the remaining resist on the substrate can be removed using known stripping procedures.

以下非限制性實例說明了本發明。 實例分子量測定: The following non-limiting examples illustrate the invention. Example molecular weight determination:

在配備有折射率偵測器Waters Alliance System GPC上使用聚苯乙烯同等值藉由凝膠滲透層析法(GPC)量測聚合物之數量及重均分子量Mn及Mw以及多分散性(PDI)值(Mw/Mn)。將樣品溶解於約1 mg/mL濃度的HPCL級THF中,並且經由四個Shodex™管柱(KF805、KF804、KF803及KF802)注射。維持1 mL/min流速及35℃溫度。用窄分子量PS標準(EasiCal PS-2,Polymer Laboratories, Inc.)校準所述管柱。溶解速率( DR )量測: Polystyrene equivalents on a Waters Alliance System GPC equipped with a refractive index detector were used to measure the number and weight average molecular weights of polymers, Mn and Mw, and polydispersity (PDI) by gel permeation chromatography (GPC). Value (Mw / Mn). The samples were dissolved in HPCL grade THF at a concentration of about 1 mg / mL and injected via four Shodex ™ columns (KF805, KF804, KF803, and KF802). Maintain a flow rate of 1 mL / min and a temperature of 35 ° C. The column was calibrated with a narrow molecular weight PS standard (EasiCal PS-2, Polymer Laboratories, Inc.). Dissolution rate ( DR ) measurement:

在TEL ACT-8晶圓軌跡上,在120℃下使8吋矽晶圓塗有底漆HMDS持續30秒,接著使用1500 rpm轉速塗佈有含有含14 wt%固體的4-甲基-2-戊醇的基質聚合物溶液,並且在90℃下軟烘烤晶圓60秒。膜厚度係在Thermawave Optiprobe量測工具上量測膜厚度並且通常係約400 nm。在LTG ARM-808EUV溶解速率監測器上在470 nm入射波長下使用0.001秒的資料收集間隔量測MF CD-26顯影劑(0.26 N水性氫氧化四甲基銨)中之溶解速率。接觸角量測 On the TEL ACT-8 wafer track, an 8-inch silicon wafer was primed with HMDS at 120 ° C for 30 seconds, and then coated with 4-methyl-2 containing 14 wt% solids at 1500 rpm. -A matrix polymer solution of amyl alcohol, and the wafer was soft baked at 90 ° C for 60 seconds. The film thickness is measured on a Thermawave Optiprobe measurement tool and is usually about 400 nm. The dissolution rate in the MF CD-26 developer (0.26 N aqueous tetramethylammonium hydroxide) was measured on a LTG ARM-808EUV dissolution rate monitor using a data collection interval of 0.001 seconds at an incident wavelength of 470 nm. Contact angle measurement

在TEL ACT-8晶圓軌跡上,在120℃下使8吋矽晶圓塗有底漆六甲基二矽氮烷(HMDS)持續30秒,塗佈有385 Å相應的面塗層組合物並且在90℃下軟烘烤60秒。在Kruss接觸角測角器上使用去離子Millipore過濾水量測面塗層組合物中之每一個的後退接觸角(RCA)。用50 μL水滴尺寸及1單位/秒的傾斜速度進行後退接觸角(RCA)量測。一旦將水滴放置在測試晶圓表面上,就立即開始晶圓台傾斜。在晶圓台傾斜期間,以每秒20幀的速率拍攝液滴的視訊直至液滴滑離其原始位置。分析視訊中之每一幀,並且當液滴剛開始滑動時的幀上的液滴影像用於利用其對應的切線來測定RCA。樹脂製備: On the TEL ACT-8 wafer track, an 8-inch silicon wafer was primed with hexamethyldisilazane (HMDS) at 120 ° C for 30 seconds and coated with a corresponding topcoat composition of 385 Å And soft-baked at 90 ° C for 60 seconds. The receding contact angle (RCA) of each of the topcoat compositions was measured on a Kruss contact angle goniometer using deionized Millipore filtered water. The receding contact angle (RCA) measurement was performed using a 50 μL water droplet size and an inclination speed of 1 unit / second. As soon as a drop of water is placed on the surface of the test wafer, the wafer table tilting begins immediately. During the tilting of the wafer table, a video of the droplet is taken at a rate of 20 frames per second until the droplet slides off its original position. Each frame in the video is analyzed, and the droplet image on the frame when the droplet just started to slide is used to determine the RCA using its corresponding tangent. Resin preparation:

使用以下單體來製備如下所述的基質聚合物及表面活性聚合物。基質聚合物( MP )合成 The following monomers were used to prepare matrix polymers and surface-active polymers as described below. . Matrix polymer ( MP ) synthesis

藉由將10 g丙二醇單甲醚(PGME)、7 g單體A1、3 g單體A2及0.50 g Wako V-601引發劑在容器中混合並攪動混合物以溶解組分來製備進料溶液。將8.6 g PGME引入反應容器中並且用氮氣吹掃容器30分鐘。接著伴以攪動將反應容器加熱至95℃。接著將進料溶液引入反應容器中並在1.5小時內進料。伴以攪動使反應容器再維持於95℃三個小時,並且接著使其冷卻至室溫。藉由將反應混合物逐滴添加至1/5甲醇/水(v/v)中來沈澱聚合物,過濾收集,並真空乾燥。得到呈白色固體粉末狀之聚合物PM1 [Mw = 12640 Da,PDI = 1.8,聚合物中之A1:A2 = 70:30 wt%]。表面活性聚合物( SAP )合成 表面活性聚合物PS1:A feed solution was prepared by mixing 10 g of propylene glycol monomethyl ether (PGME), 7 g of monomer A1, 3 g of monomer A2, and 0.50 g of Wako V-601 initiator in a container and stirring the mixture to dissolve the components. 8.6 g of PGME was introduced into the reaction vessel and the vessel was purged with nitrogen for 30 minutes. The reaction vessel was then heated to 95 ° C with agitation. The feed solution was then introduced into the reaction vessel and fed within 1.5 hours. The reaction vessel was maintained at 95 ° C for another three hours with agitation, and then allowed to cool to room temperature. The polymer was precipitated by dropwise addition of the reaction mixture to 1/5 methanol / water (v / v), collected by filtration, and dried under vacuum. The polymer PM1 was obtained as a white solid powder [Mw = 12640 Da, PDI = 1.8, A1: A2 = 70:30 wt% in the polymer]. Surface-active polymer ( SAP ) synthesis Surface-active polymer PS1:

在圓底燒瓶中添加90 g丙二醇甲醚乙酸酯(PGMEA)及1.54 g Wako V-601引發劑,隨後添加24.71 g單體M1及3.77 g單體M2。藉由伴以攪拌在氮氣下吹掃15分鐘使無色溶液脫氧。攪拌反應混合物並加熱至85℃持續18小時。接著使反應混合物冷卻至室溫。藉由將反應混合物逐滴添加至1:4甲醇:水(v:v)中來沈澱聚合物,過濾收集,並真空乾燥。由此形成表面活性聚合物PS1。[Mw = 31090 Da,PDI = 2.45]。 表面活性聚合物PS2-PS6及CP1-CP3(比較):In a round bottom flask, 90 g of propylene glycol methyl ether acetate (PGMEA) and 1.54 g of Wako V-601 initiator were added, followed by 24.71 g of monomer M1 and 3.77 g of monomer M2. The colorless solution was deoxygenated by purging with stirring for 15 minutes under nitrogen. The reaction mixture was stirred and heated to 85 ° C for 18 hours. The reaction mixture was then allowed to cool to room temperature. The polymer was precipitated by adding the reaction mixture dropwise to 1: 4 methanol: water (v: v), collected by filtration, and dried under vacuum. Thus, a surface-active polymer PS1 was formed. [Mw = 31090 Da, PDI = 2.45]. Surface-active polymers PS2-PS6 and CP1-CP3 (comparative):

表面活性聚合物PS2-PS6及CP1-CP3(比較)係用類似於用於表面活性聚合物PS1程序的程序合成的。對於聚合物中之每一種,表1示出了結構單元、如由1 H NMR(600 MHz)測定的組成比、重均分子量及分散性(Mw/Mn)。 表1 Comp=比較實例,RCA=後退接觸角 面塗層添加劑The surface-active polymers PS2-PS6 and CP1-CP3 (comparative) were synthesized using a procedure similar to that used for the surface-active polymer PS1 procedure. For each of the polymers, Table 1 shows the structural units, composition ratios, weight average molecular weights, and dispersibility (Mw / Mn) as determined by 1 H NMR (600 MHz). Table 1 Comp = comparative example, RCA = retracted contact angle surface coating additive

使用以下小分子添加劑B1及C1來製備如下所述的面塗層組合物。 面塗層組合物製備 The following small molecule additives B1 and C1 were used to prepare a top coating composition as described below. Preparation of top coating composition

藉由將表2中所示的組分添加至包含呈如表2中所述量的4-甲基-2-戊醇、異丁酸異丁酯及二丙二醇甲醚之溶劑系統中來配製面塗層組合物。將每種混合物過濾通過0.2 μm PTFE盤。 表2 Comp=比較實例;4M2P=4-甲基-2-戊醇;IBIB=異丁酸異丁酯;DPM=二丙二醇甲醚。所有值以公克(g)為單位。光微影及圖案缺陷測試 Formulated by adding the components shown in Table 2 to a solvent system containing 4-methyl-2-pentanol, isobutyl isobutyrate, and dipropylene glycol methyl ether in the amounts described in Table 2 Topcoat composition. Each mixture was filtered through a 0.2 μm PTFE dish. Table 2 Comp = comparative example; 4M2P = 4-methyl-2-pentanol; IBIB = isobutyl isobutyrate; DPM = dipropylene glycol methyl ether. All values are in grams (g). Photolithography and pattern defect test

使用TEL Lithius 300 mm晶圓軌跡及ASML 1900i浸沒式掃描儀在1.35 NA、0.85/0.75內/外σ及具有X偏振的偶極子35Y照射下進行圖案缺陷測試。使用205℃固化持續60秒使300 mm裸Si晶圓塗佈有AR™40A抗反射劑(陶氏化學公司(The Dow Chemical Company))以形成800 Å厚的第一底部抗反射塗層(BARC)。使用175℃固化持續60秒將AR™104抗反射劑(陶氏化學公司)施用於第一BARC層上以形成400 Å厚的第二BARC層。將EPIC™2099光阻劑(陶氏化學公司)施用於BARC疊層上並在95℃下軟烘烤60秒以形成950 Å厚之光阻劑層。使光阻劑層塗佈有相應的面塗層組合物TC1-TC4並在90℃下軟烘烤60秒至385 Å的厚度。在浸沒式掃描儀上使晶圓暴露成45 nm 1:1線/空間圖案並在95℃下暴露後烘烤60秒。在暴露後烘烤後,將晶圓在0.26 N水性TMAH顯影劑中在20秒循環中顯影,用蒸餾水沖洗,並旋轉乾燥。在KLA-Tencor 2800缺陷檢查工具上檢查圖案化晶圓。表3中提供了缺陷分析的結果。 表3 The pattern defect test was performed using a TEL Lithius 300 mm wafer trace and an ASML 1900i immersion scanner under 1.35 NA, 0.85 / 0.75 inner / outer σ, and dipole 35Y with X polarization. 300 mm bare Si wafers were coated with AR ™ 40A antireflection agent (The Dow Chemical Company) using 205 ° C curing for 60 seconds to form a 800 Å first bottom antireflection coating (BARC) ). AR ™ 104 antireflection agent (The Dow Chemical Company) was applied to the first BARC layer using a 175 ° C cure for 60 seconds to form a 400 Å thick second BARC layer. EPIC ™ 2099 photoresist (The Dow Chemical Company) was applied to the BARC stack and soft baked at 95 ° C for 60 seconds to form a 950 Å thick photoresist layer. The photoresist layer was coated with the corresponding top coating composition TC1-TC4 and soft-baked at 90 ° C for 60 seconds to a thickness of 385 Å. The wafer was exposed to a 45 nm 1: 1 line / space pattern on an immersion scanner and baked for 60 seconds after exposure at 95 ° C. After baking after exposure, the wafers were developed in a 0.26 N aqueous TMAH developer in a 20 second cycle, rinsed with distilled water, and spin-dried. Inspect patterned wafers on KLA-Tencor 2800 defect inspection tool. The results of the defect analysis are provided in Table 3. table 3

Claims (10)

一種光阻劑面塗層組合物,其包括: 第一聚合物,其係水性鹼溶性的並且以所述組合物之總固體計以70至99 wt%之量存在; 第二聚合物,其包括具有通式(IV)之重複單元及具有通式(V)之重複單元:其中:R5 獨立地表示H、鹵素原子、C1-C3烷基或C1-C3鹵烷基;R6 表示直鏈、分支鏈或環狀C1至C20氟烷基;R7 表示直鏈、分支鏈或環狀C1至C20氟烷基;L3 表示多價連接基團;並且m係1至5之整數;其中所述第二聚合物不含非氟化側鏈;並且其中所述第二聚合物之存在量以所述組合物之總固體計係1至30 wt%;及 溶劑。A photoresist top coating composition comprising: a first polymer that is water-soluble and alkali-soluble and is present in an amount of 70 to 99 wt% based on the total solids of the composition; a second polymer that Including repeating units with general formula (IV) and repeating units with general formula (V): Wherein: R 5 independently represents H, halogen atom, C1-C3 alkyl or C1-C3 haloalkyl; R 6 represents straight, branched or cyclic C1 to C20 fluoroalkyl; R 7 represents straight, branched Chain or cyclic C1 to C20 fluoroalkyl; L 3 represents a polyvalent linking group; and m is an integer from 1 to 5; wherein the second polymer does not contain non-fluorinated side chains; and wherein the second The polymer is present in an amount of 1 to 30 wt% based on the total solids of the composition; and a solvent. 如申請專利範圍第1項所述之光阻劑面塗層組合物,其中L3 表示-C(O)OCH2-。The photoresist top coating composition according to item 1 of the scope of the patent application, wherein L 3 represents -C (O) OCH2-. 如申請專利範圍第1項或第2項所述之光阻劑面塗層組合物,其中R6 係分支鏈的。The photoresist top coating composition according to item 1 or item 2 of the patent application scope, wherein R 6 is branched. 如申請專利範圍第1項至第3項中任一項所述之光阻劑面塗層組合物,其中R6 係全氟化的。The photoresist top coating composition according to any one of claims 1 to 3 in the scope of the patent application, wherein R 6 is perfluorinated. 如申請專利範圍第1項至第4項中任一項所述之光阻劑面塗層組合物,其中所述第一聚合物包括具有通式(I)之重複單元及具有通式(II)之重複單元:其中:R1 獨立地表示H、鹵素原子、C1-C3烷基或C1-C3鹵烷基;R2 表示視情況經取代之直鏈、分支鏈或環狀C1-C20烷基;L1 表示單鍵或多價連接基團;並且n係1至5之整數。The photoresist surface coating composition according to any one of claims 1 to 4 in the scope of the patent application, wherein the first polymer includes a repeating unit having the general formula (I) and a unit having the general formula (II) ) Repeating unit: Wherein: R 1 independently represents H, a halogen atom, a C1-C3 alkyl group, or a C1-C3 haloalkyl group; R 2 represents a linear, branched, or cyclic C1-C20 alkyl group optionally substituted; L 1 represents A single bond or a multivalent linking group; and n is an integer from 1 to 5. 如申請專利範圍第1項至第5項中任一項所述之光阻劑面塗層組合物,其中所述第一聚合物包括具有通式(III)之重複單元:其中:R3 選自H、鹵素原子、C1-C3烷基或C1-C3鹵烷基;R4 獨立地選自經取代或未經取代之C1-C12烷基或經取代或未經取代之C5-C18芳基;X係C2-C6經取代或未經取代之伸烷基;其中X可以視情況包括一個或多個環並且與R4 一起可以視情況形成環;L2 係單鍵或連接基團;p係1至50之整數;並且q係1至5之整數。The photoresist top coating composition according to any one of claims 1 to 5, wherein the first polymer includes a repeating unit having the general formula (III): Wherein: R 3 is selected from H, halogen atom, C1-C3 alkyl or C1-C3 haloalkyl; R 4 is independently selected from substituted or unsubstituted C1-C12 alkyl or substituted or unsubstituted C5-C18 aryl; X is C2-C6 substituted or unsubstituted alkylene; where X may optionally include one or more rings and together with R 4 may optionally form a ring; L 2 is a single bond or Linking group; p is an integer from 1 to 50; and q is an integer from 1 to 5. 如申請專利範圍第1項至第6項中任一項所述之光阻劑面塗層組合物,其中所述溶劑係基於有機物之溶劑。The photoresist top coating composition according to any one of claims 1 to 6, wherein the solvent is an organic-based solvent. 一種經塗佈基板,其包括: 基板上之光阻劑層;及 所述光阻劑層上的由如申請專利範圍第1項至第7項中任一項所述之光阻劑面塗層組合物形成之面塗層。A coated substrate comprising: a photoresist layer on the substrate; and a photoresist surface coating on the photoresist layer as described in any one of claims 1 to 7 of the scope of patent application. A topcoat formed by the layer composition. 一種處理光阻劑組合物之方法,其包括: (a) 將光阻劑組合物施用於基板上以形成光阻劑層; (b) 在所述光阻劑層上施用如申請專利範圍第1項至第7項中任一項所述之光阻劑面塗層組合物以形成面塗層; (c) 使所述面塗層及所述光阻劑層暴露於活化輻射;並且 (d) 使所述經暴露面塗層及光阻劑層與顯影劑接觸以形成抗蝕劑圖案。A method for processing a photoresist composition, comprising: (a) applying a photoresist composition to a substrate to form a photoresist layer; (b) applying on the photoresist layer as described in the patent application The photoresist topcoat composition of any one of items 1 to 7 to form a topcoat; (c) exposing the topcoat and the photoresist layer to activating radiation; and ( d) contacting the exposed surface coating layer and the photoresist layer with a developer to form a resist pattern. 如申請專利範圍第9項所述之,其中所述面塗層藉由旋塗形成,並且所述第二聚合物在所述旋塗期間遷移至所述面塗層之上表面上,其中所述面塗層之上表面基本上由所述第二聚合物組成。As described in item 9 of the scope of patent application, wherein the top coat is formed by spin coating, and the second polymer migrates to the top surface of the top coat during the spin coating, wherein The top surface of said topcoat consists essentially of said second polymer.
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